Aliphatic polyester coating compositions containing tetramethyl cyclobutanediol

ABSTRACT

Disclosed are aliphatic polyester resins containing 2,2,4,4-tetramethyl-1,3-cyclobutanediol and solvent borne, thermosetting coating compositions prepared therefrom. The aliphatic polyesters exhibit good hardness and flexibility when formulated into thermosetting coatings compositions.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.12/367,190, filed on Feb. 6, 2009, the disclosure of which isincorporated herein by reference in its entirety.

FIELD OF THE INVENTION

This invention pertains to aliphatic, curable polyesters forsolvent-borne, thermosetting coating compositions. More particularly,this invention pertains to curable polyesters containing2,2,4,4-tetramethyl-1,3-cyclobutanediol and high-solids, solvent-bornethermosetting coating compositions prepared from these polyesters. Thesepolyesters can be used in blends with acrylic resins or serve as theprimary film former in a coating formulation.

BACKGROUND OF THE INVENTION

Solvent-borne, polyester thermosetting coatings that exhibit highhardness are desirable. Coatings with high hardness typically exhibithigh gloss, good distinctness of image (DOI), fast dry-times, scratch,stain, chemical, and humidity resistance, and outdoor durability.

Aliphatic polyesters are frequently used to reduce viscosity andincrease solids for thermosetting acrylic (abbreviated herein as “TSA”)coatings. Aliphatic polyesters also are useful as a primary film formerin high solids coatings because of their ability to reduce volatileorganic compound (“VOC”) emissions. Coatings made from aliphaticpolyesters are generally flexible but tend to be soft, which results inpoor resistance to solvents and chemicals, poor humidity resistance andpoor outdoor durability.

Hardness and hardness-related properties of aliphatic polyester resinssometimes can be improved with the addition of 1,4-cyclohexanedimethanol(abbreviated herein as “CHDM”) and hydrogenated bisphenol A (abbreviatedherein as “HBPA”). Unfortunately, poor solvent solubility andcompatibility with acrylic resins often are observed as CHDM content isincreased in the polyester resin formulation. The amount of CHDM thatcan be incorporated into the resin formulation, therefore is limited.HBPA is know to exhibit similar characteristics.

Poor resin solubility often manifests itself over time by phaseseparation, precipitation of the resin from solution, and thedevelopment of hazy to opaque resin solutions. These characteristics areundesirable and limit the storage stability of the resin solution andthe coatings formulated from these solutions. Such coatings, forexample, may experience a viscosity increase, phase separation,agglomeration of ingredients, etc., that result in an undesirable higherapplication viscosity, poor appearance and poor mechanical properties ofthe cured film.

Thermosetting acrylic (“TSA”) resins are widely used in industrialcoatings. They can be formulated to a high glass transition temperature(Tg) and exhibit excellent light stability and hydrolysis resistance.These properties result in coatings with the desirable characteristicsof high hardness; fast dry times; resistance to stains, chemicals andhumidity; and good outdoor durability. Consequently, TSA resins oftenserve as the primary film-former in coatings for demanding applicationsthat include transportation, maintenance, marine andbuilding/construction markets.

Although TSA resins exhibit many desirable properties, they often lackflexibility and require more solvent in the coating formulation toachieve a practical application viscosity. The higher solventrequirement for TSA resins makes it difficult to achieve high solidscoatings with reduced VOC content as mandated by various federal andstate air quality organizations.

To increase resin and coating solids, reduce viscosity, and lower VOCemission, aliphatic polyester resins can be blended with TSA resins.Unfortunately, the glass transition temperature (“Tg”) of the blendfrequently decreases significantly as the polyester content increases.The lower Tg of the blend has an adverse impact on the desirablecharacteristics that the TSA resin imparts to the coating.

There is a need in the coatings industry for aliphatic polyesters thatexhibit good hardness with good flexibility and solubility whenformulated into thermosetting coatings compositions. In addition, thereis a need for aliphatic polyester resins that, when blended with TSAresins, lower the viscosity while maintaining the Tg of the TSA resin inhigh solids, thermosetting coating compositions.

SUMMARY OF THE INVENTION

The present invention provides curable, aliphatic polyesters preparedfrom 2,2,4,4-tetramethyl-1,3-cyclobutanediol. Thus, one embodiment ofour invention is a curable, aliphatic polyester, comprising:

-   i. diacid residues, comprising at least 90 mole percent, based on    the total moles of diacid residues, of the residues of at least one    aliphatic diacid, the aliphatic dicarboxylic acid comprising about    50 to 100 mole percent of a cycloaliphatic dicarboxylic acid;-   ii. diol residues, comprising about 50 to 100 mole percent, based on    the total moles of diol residues, of the residues of    2,2,4,4-tetramethyl-1,3-cyclobutanediol; and-   iii. about 2 to about 40 mole percent of the residues of at least    one polyol, based on the total moles of diol and polyol residues;    wherein the curable, aliphatic polyester has a number average    molecular weight of about 300 to about 10,000 daltons, a glass    transition temperature of about −35° C. to about 35° C., a hydroxyl    number of about 20 to about 450 mg KOH/g of polyester, and an acid    number of 0 to about 80 mg KOH/g of polyester.

Coatings formulated from these all aliphatic polyester resins canexhibit high gloss, distinctness of image and reflectivity; goodhardness with good flexibility; solvent and chemical resistance; andgood gloss retention during UV and humidity exposure for good outdoordurability. Thus, another embodiment of our invention is a thermosettingcoating composition, comprising:

-   (A). about 50 to about 90 weight percent, based on the total weight    of (A) and (B) of at least one curable, aliphatic polyester,    comprising    -   i. diacid residues, comprising at least 90 mole percent, based        on the total moles of diacid residues, of the residues of at        least one aliphatic diacid, the aliphatic dicarboxylic acid        comprising about 50 to 100 mole percent of a cycloaliphatic        dicarboxylic acid;    -   ii. diol residues, comprising about 50 to 100 mole percent,        based on the total moles of diol residues, of the residues of        2,2,4,4-tetramethyl-1,3-cyclobutanediol; and    -   iii. about 2 to about 40 mole percent of the residues of at        least one polyol, based on the total moles of diol and polyol        residues;    -   wherein the curable, aliphatic polyester has a number average        molecular weight of about 300 to about 10,000 daltons, a glass        transition temperature of about −35° C. to about 35° C., a        hydroxyl number of about 20 to about 450 mg KOH/g of polyester,        and an acid number of 0 to about 80 mg KOH/g of polyester;-   (B). about 10 to about 50 weight percent, based on the total weight    of (A) and (B) of a crosslinker comprising at least one compound    reactive with a carboxylic acid or a hydroxyl group;-   (C). about 10 to about 60 weight percent, based on the total weight    of (A), (B), and (C) of at least one nonaqueous solvent.

The aliphatic polyesters may be blended with acrylics or serve as theprimary film former to formulate factory and field-applied coatings usedin auto OEM, auto refinish, transportation, aerospace, maintenance,marine, machinery and equipment, general metal, appliance, metalfurniture, plastic and building/construction applications. When blendedwith thermosetting acrylic (TSA) resins, our aliphatic polyestersexhibit good solubility, compatibility and viscosity reduction with goodTg retention of the blend.

DETAILED DESCRIPTION

We have found that curable, aliphatic polyesters that contain2,2,4,4-tetramethyl-1,3-cyclobutanediol (abbreviated herein as “TMCD”)can be used to prepare solvent-borne, high-solids, thermosettingcoatings that exhibit high gloss, good hardness and flexibility; andsolvent and chemical resistance. These aliphatic polyesters also can beblended with thermosetting acrylic resins (“TSA”) to produce blends thathave low viscosity, good compatibility, flexibility, and Tg retention.Thus, in a general embodiment, our invention provides a curable,aliphatic polyester, comprising:

-   i. diacid residues, comprising at least 90 mole percent, based on    the total moles of diacid residues, of the residues of at least one    aliphatic diacid, the aliphatic dicarboxylic acid comprising about    50 to 100 mole percent of a cycloaliphatic dicarboxylic acid;-   ii. diol residues, comprising about 50 to 100 mole percent, based on    the total moles of diol residues, of the residues of    2,2,4,4-tetramethyl-1,3-cyclobutanediol; and-   iii. about 2 to about 40 mole percent of the residues of at least    one polyol, based on the total moles of diol and polyol residues;    wherein the curable, aliphatic polyester has a number average    molecular weight of about 300 to about 10,000 daltons, a glass    transition temperature of about −35° C. to about 35° C., a hydroxyl    number of about 20 to about 450 mg KOH/g of polyester, and an acid    number of 0 to about 80 mg KOH/g of polyester. Another aspect of the    invention is a solvent borne thermosetting coating formulation    comprising the above aliphatic polyester resin. The coating    formulation may, optionally, comprise a crosslinker, various    additives and pigments.

Unless otherwise indicated, all numbers expressing quantities ofingredients, properties such as molecular weight, reaction conditions,and so forth used in the specification and claims are to be understoodas being modified in all instances by the term “about.” Unless indicatedto the contrary, the numerical parameters set forth in the followingspecification and attached claims are approximations that may varydepending upon the desired properties sought to be obtained by thepresent invention. At the very least, each numerical parameter should beconstrued in light of the number of reported significant digits and byapplying ordinary rounding techniques. Further, the ranges stated inthis disclosure and the claims are intended to include the entire rangespecifically and not just the endpoint(s). For example, a range statedto be 0 to 10 is intended to disclose all whole numbers between 0 and 10such as, for example 1, 2, 3, 4, etc., all fractional numbers between 0and 10, for example 1.5, 2.3, 4.57, 6.1113, etc., and the endpoints 0and 10. Also, a range associated with chemical substituent groups suchas, for example, “C₁ to C₅ diols”, is intended to specifically includeand disclose C₁ and C₅ diols as well as C₂, C₃, and C₄ diols.

Notwithstanding that the numerical ranges and parameters setting forththe broad scope of the invention are approximations, the numericalvalues set forth in the specific examples are reported as precisely aspossible. Any numerical value, however, inherently contains certainerrors necessarily resulting from the standard deviation found in itsrespective testing measurements.

As used in the specification and the appended claims, the singular forms“a,” “an” and “the” include their plural referents unless the contextclearly dictates otherwise. For example, a reference to a “polyester,” a“dicarboxylic acid”, a “residue” is synonymous with “at least one” or“one or more” polyesters, dicarboxylic acids, or residues and is thusintended to refer to both a single or plurality of polyesters,dicarboxylic acids, or residues. In addition, references to acomposition containing or including “an” ingredient or “a” polyester isintended to include other ingredients or other polyesters, respectively,in addition to the one named. The terms “containing” or “including” areintended to be synonymous with the term “comprising”, meaning that atleast the named compound, element, particle, or method step, etc., ispresent in the composition or article or method, but does not excludethe presence of other compounds, catalysts, materials, particles, methodsteps, etc, even if the other such compounds, material, particles,method steps, etc., have the same function as what is named, unlessexpressly excluded in the claims.

Also, it is to be understood that the mention of one or more processsteps does not preclude the presence of additional process steps beforeor after the combined recited steps or intervening process steps betweenthose steps expressly identified. Moreover, the lettering of processsteps or ingredients is a convenient means for identifying discreteactivities or ingredients and the recited lettering can be arranged inany sequence, unless otherwise indicated.

The term “curable, aliphatic polyester”, as used herein, is synonymouswith the term “resin” and is intended to mean a thermosetting surfacecoating polymer prepared by the polycondensation of one or more acidcomponents, diol components, and polyol components. The curable,aliphatic polyester of the present invention is a thermoset polymer andis suitable as a resin for solvent-based coatings. This polyester has alow molecular weight, typically about 300 to about 10,000 daltons, andwould not be suitable for the fabrication films, sheets, and othershaped objects by extrusion, casting, blow molding, and otherthermoforming processes commonly used for high molecular weightthermoplastic polymers. The polyester has a reactive functional group,typically a hydroxyl group or carboxyl group for the purpose of laterreacting with a crosslinker in a coating formulation. The functionalgroup is controlled by having either excess diol or acid (fromdicarboxylic acid or tricarboxylic acid) in the polyester resincomposition. The desired crosslinking pathway will determine whether thepolyester resin will be hydroxyl-terminated or carboxylicacid-terminated. This concept is known to those skilled in the art anddescribed, for example, in Organic Coatings Science and Technology, 2nded., p. 246-257, by Z. Wicks, F. Jones, and S. Pappas, Wiley, New York,1999.

Typically, the acid component comprises at least one dicarboxylic acidand may, optionally, include mono- and polybasic carboxylic acids. Forexample, the curable, aliphatic polyester may be prepared from an acidcomponent comprising an aliphatic or cycloaliphatic dicarboxylic acidsuch as, for example, adipic acid or 1,3-cyclohexanedicarboxylic acid,or a mixture of one or more aliphatic and cycloaliphatic acids. The diolcomponent may comprise one or more cycloaliphatic diols such as, forexample, 2,2,4,4-tetramethyl-1,3-cyclobutanediol, either alone or incombination with one or more linear or branched aliphatic diols such as,for example, neopentyl glycol. Catalysts may be used to accelerate therate of the polycondensation reaction. Additional examples of each ofthe components of the curable, aliphatic polyester include those knownin the art including, but not limited to, those discussed below, and invarious documents known in the art such as, for example, in Resins forSurface Coatings, Vol. III, p. 63-167, ed. by P. K. T. Oldring and G.Hayward, SITA Technology, London, UK, 1987.

The term “residue”, as used herein in reference to the polymers of theinvention, means any organic structure incorporated into a polymerthrough a polycondensation or ring opening reaction involving thecorresponding monomer. It will also be understood by persons havingordinary skill in the art, that the residues associated within thevarious curable polyesters of the invention can be derived from theparent monomer compound itself or any derivative of the parent compound.For example, the dicarboxylic acid residues referred to in the polymersof the invention may be derived from a dicarboxylic acid or itsassociated acid halides, esters, salts, anhydrides, or mixtures thereof.Thus, as used herein, the term “dicarboxylic acid” is intended toinclude dicarboxylic acids and any derivative of a dicarboxylic acid,including its associated acid halides, esters, half-esters, salts,half-salts, anhydrides, mixed anhydrides, or mixtures thereof, useful ina polycondensation process with a diol to make a curable, aliphaticpolyester.

The term “aliphatic” is intended to have its common meaning as would beunderstood by persons having ordinary skill in the art, that is, acyclicor cyclic, saturated or unsaturated carbon compounds, excludingbenzenoid or other aromatic systems. The term “cycloaliphatic”, as usedherein, is intended to mean an aliphatic, cyclic compound. The term“aliphatic polyester”, as used herein, is understood to mean a polyesterthat contains 90 or greater mole percent aliphatic diacid or diolresidues, based on the total moles of diacid or diol residues. Smallamounts (i.e., 10 mole percent or less) of aromatic dicarboxylic acidsor aromatic diols also may be present.

The curable, aliphatic polyester comprises diacid residues, thatcomprise at least 90 mole percent, based on the total moles of diacidresidues, of the residues of at least one aliphatic diacid which, inturn, comprises about 50 to 100 mole percent of a cycloaliphaticdicarboxylic acid. Some examples of aliphatic and cycloaliphaticdicarboxylic acids include, but are not limited to, adipic acid,dodecanedioic acid, sebacic acid, azelaic acid,1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid,hexahydrophthalic anhydride, tetrahydrophthalic anhydride succinic acid,glutaric acid, and combinations thereof. For example, the curable,aliphatic polyester can comprise about 50 mole percent of the residuesof 1,4-cyclohexanedicarboxylic acid and about 50 mole percent of theresidues of adipic acid, based on the total moles of diacid residues. Inanother example, the curable, aliphatic polyester can contain about 50mole percent of the residues of hexahydrophthalic anhydride and about 50mole percent of the residues of adipic acid.

Some additional, non-limiting examples of the diacid component of thecurable, aliphatic polyester are as follows: (a) about 50 to about 85mole percent of the residues of at least one diacid chosen from1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid,hexahydrophthalic anhydride, and combinations thereof; and about 15 toabout 50 mole percent of the residues of at least one alicyclicaliphatic diacid having from 4 to 10 carbon atoms; (b) about 50 to about85 mole percent of the residues of at least one diacid chosen from1,4-cyclohexanedicarboxylic acid, hexahydrophthalic anhydride, andcombinations thereof; and about 15 to about 50 mole percent of theresidues of at least one diacid chosen from adipic acid, succinic acid,and glutaric acid; (c) about 50 to about 75 mole percent of the residuesof at least one diacid chosen from 1,4-cyclohexanedicarboxylic acid,hexahydrophthalic anhydride, and combinations thereof; and about 25 toabout 50 mole percent of the residues of at least one diacid chosen fromadipic acid, succinic acid, and glutaric acid; (d) about 50 to about 65mole percent of the residues of at least one diacid chosen from1,4-cyclohexanedicarboxylic acid, hexahydrophthalic anhydride, andcombinations thereof; and about 35 to about 50 mole percent of theresidues of at least one diacid chosen from adipic acid, succinic acid,and glutaric acid; (e) about 50 mole percent of the residues of one ordiacids chosen from 1,4-cyclohexanedicarboxylic acid, hexahydrophthalicanhydride, and combinations thereof; and about 50 mole percent of theresidues of adipic acid; and (f) about 50 mole percent of the residuesof 1,4-cyclohexanedicarboxylic acid and about 50 mole percent of theresidues of adipic acid. In addition to the residues of alicyclic andcyclic aliphatic dicarboxylic acids described above, the diacid residuesmay further comprise from 0 to about 10 mole percent of the residues ofat least one aromatic dicarboxylic acid chosen from phthalic acid,terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid,and combinations thereof.

In addition to the aliphatic diacid residues described above, the acidcomponent of our inventive polyester composition may further comprisethe residues of a monocarboxylic acid or a polybasic acid containingmore that 2 carboxylic acid groups. For example, the curable, aliphaticpolyester may comprise residues of at least one monocarboxylic acid or apolybasic acid chosen from benzoic acid, acetic acid, 2-ethyl-hexanoicacid, propionic acid, tert-butyl benzoic acid, and butanoic acid;trimellitic anhydride; or a mixture thereof. In another example, theacid component can comprise the residues of at least one aliphatictricarboxylic acid such as, for example, 1,2,4-cyclohexanetricarboxylicacid, 1,3,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid,and mixtures of one or more of these acids.

The curable, aliphatic polyester also comprises the residues of2,2,4,4-tetramethyl-1,3-cyclobutanediol (“TMCD”). For example, thecurable, aliphatic polyester can comprise about 50 to 100 mole percentTMCD, based on the total moles of diol residues. Other representativeexamples of TMCD concentrations, are about 75 to 100 mole percent, andabout 85 to 100 mole percent.

Other aliphatic diols, in addition to TMCD, can be used to prepare thecurable, aliphatic polyester of the instant invention. Representativeexamples of aliphatic diols include, but are not limited to, neopentylglycol, ethylene glycol, propylene glycol, diethylene glycol,triethylene glycol, tetraethylene glycol, pentaethylene glycol,hexaethylene glycol, heptaethylene glycol, octaethylene glycol,nonaethylene glycol, decaethylene glycol, 1,3-propanediol,2,4-dimethyl-2-ethyl-hexane-1,3-diol, 2,2-dimethyl-1,2-propanediol,2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol,1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol,1,6-hexanediol, 2-ethyl-1,3-hexanediol,2,2,4,4-tetramethyl-1,6-hexanediol, thiodiethanol,1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol,1,4-cyclohexanedimethanol, 2,2,4-trimethyl 1,3-pentanediol,2,4-diethyl-1,5-pentanediol, hydroxypivalyl hydroxypivalate,1,10-decanediol and hydrogenated bisphenol A. For example, in oneembodiment, the curable, aliphatic polyester resins comprise acombination of the residues of neopentyl glycol and TMCD. It should beunderstood that the diols listed above may be used in any combinationwith TMCD and the aforementioned diacid components and in any amountwithin the ranges described hereinabove

For example, in one embodiment, the curable, aliphatic polyester cancomprise (i) diacid residues comprising about 50 to about 85 molepercent of the residues of at least one cycloaliphatic dicarboxylic acidchosen from 1,4-cyclohexanedicarboxylic acid,1,3-cyclohexanedicarboxylic acid, hexahydrophthalic anhydride, and about15 to about 50 mole percent of the residues at least one acylicaliphatic dicarboxylic acid chosen from dodecanedioic acid, adipic acid,sebacic acid, azelaic acid, maleic acid, fumaric acid, succinic acid,and glutaric acid; and (ii) diol residues comprising about 50 to 100mole percent of the residues of TMCD and about 50 to 0 mole percent ofthe residues of at least one diol chosen from neopentyl glycol, ethyleneglycol, propylene glycol, diethylene glycol, triethylene glycol,tetraethylene glycol, pentaethylene glycol, hexaethylene glycol,heptaethylene glycol, octaethylene glycol, nonaethylene glycol,decaethylene glycol, 1,3-propanediol,2,4-dimethyl-2-ethyl-hexane-1,3-diol, 2,2-dimethyl-1,2-propanediol,2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol,1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol,2,2,4-trimethyl-1,6-hexanediol, thiodiethanol,1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol,1,4-cyclohexanedimethanol, 2,2,4-trimethyl 1,3-pentanediol,p-xylenediol, hydroxypivalyl hydroxypivalate, 1,10-decanediol, andhydrogenated bisphenol A. In another example, the curable aliphaticpolyester can comprise (i) diacid residues comprising about 50 to about85 mole percent of the residues of 1,4-cyclohexanedicarboxylic acid,hexahydrophthalic anhydride, or a mixture thereof, and about 15 to about50 mole percent of the residues of adipic acid; and (ii) diol residuescomprising about 50 to 100 mole percent of the residues of TMCD andabout 50 to 0 mole percent of the residues of neopentyl glycol. In yetanother example, the curable, aliphatic polyester can comprise (i)diacid resides comprising about 50 mole percent of the residues ofhexahydrophthalic anhydride and about 50 mole percent of the residues ofadipic acid; and (ii) diol residues comprising about 75 to 100 molepercent of the residues of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, andabout 25 to 0 mole percent of the residues of neopentyl glycol.

In addition to diacid and diol residues, the curable, aliphaticpolyester comprises about 2 to about 40 mole percent of the residues ofat least one polyol, based on the total moles of diol and polyolresidues. These polyols may include aliphatic, alicyclic, and cyclicalkyl polyols. Some specific examples of polyols include, but are notlimited to, trimethylolpropane (abbreviated herein as “TMP),pentaerythritol (abbreviated herein as “PE”), trimethylolethane(abbreviated herein as “TME”), erythritol, threitol, dipentaerythritol,sorbitol, glycerine, and the like. In one example, the curable,aliphatic polyester can comprise about 3 to about 30 mole percent of theresidues of at least one polyol selected from trimethylolpropane,pentaerythritol, trimethylolethane, erythritol, threitol,dipentaerythritol, sorbitol, and glycerine. In another embodiment, thecurable, aliphatic polyester comprises trimethylolpropane.

The curable, aliphatic polyester of this invention has a hydroxyl numberof about 20 to about 450 mg KOH/g resin. Further examples of hydroxylnumber are about 25 to about 300, and about 30 to about 250. Inaddition, the curable, aliphatic polyester has an acid number of about 0to about 80 mg KOH/g polyester or, in other examples, about 2 to about25 mg KOH/g polyester, and about 2 to about 15 mg KOH/g polyester. Thenumber average molecular weight of the curable, aliphatic polyester isabout 300 daltons to about 10,000 daltons. Additional examples ofmolecular weight ranges are about 400 to about 7000, and about 500 toabout 5000. The curable, aliphatic polyester has a glass transitiontemperature (abbreviated herein as “Tg”) of about −35 to about 35° C.Some additional, representative examples of Tg ranges for the curable,aliphatic polyester are about −35 to about 30° C., about −35 to about25° C., about −35 to less than 20, about −35 to about 19° C., about −35to about 18° C., about −35 to about 17° C., about −35 to about 16° C.,about −35 to about 15° C., about −35 to about 10° C. For example, thecurable, aliphatic polyester can have a hydroxyl number of about 30 toabout 250 mg potassium hydroxide per gram of polyester, an acid numberof about 2 to about 15 mg potassium hydroxide per gram of polyester, anda number average molecular weight of about 700 to about 7000 daltons,and a Tg of about −20 to about 20° C.

A further aspect of the invention is a curable, aliphatic polyester,consisting essentially of:

-   i. diacid residues, consisting essentially of the residues of at    least one aliphatic diacid, the aliphatic dicarboxylic acid    comprising about 50 to 100 mole percent, based on the total moles of    diacid residues, of a cycloaliphatic dicarboxylic acid selected from    residues of 1,4-cyclohexanedicarboxylic acid, hexahydrophthalic    anhydride, or a mixture thereof;-   ii. diol residues, consisting essentially of about 75 to 100 mole    percent, based on the total moles of diol residues, of the residues    of 2,2,4,4-tetramethyl-1,3-cyclobutanediol;-   iii. about 2 to about 40 mole percent of the residues of at least    one polyol, based on the total moles of diol and polyol residues;    wherein the curable, aliphatic polyester has a number average    molecular weight of about 300 to about 10,000 daltons, a glass    transition temperature of about −35° C. to about 35° C., a hydroxyl    number of about 20 to about 450 mg KOH/g of polyester, and an acid    number of 0 to about 80 mg KOH/g of polyester.

The phrase “consisting essentially of”, as used herein is intended toencompass curable polyesters having components (i)-(iii) listed aboveand is understood to exclude any elements that would substantially alterthe essential properties of the polyester to which the phrase refers.For example, the diacid and diol residues may include other componentsthat do not alter the solubility of the curable, aliphatic polyester andits compatibility with TSA resins. For example, any combination of diol,diacid, and polyol monomers that would produce a resin having a Tggreater than about 45° C. would be understood in the art to reduce thatsolubility of a polyester polymer would be excluded from thisembodiment. Some representative classes of diacids and diols that wouldbe expected to increase Tg and reduce solubility include, but are notlimited to, cycloaliphatic diol or diacid components, andpolycycloaliphatic diacids or diols. Some examples of diacid and diolcomponents that would be excluded from this embodiment are hydrogenatedbisphenol A at 50 mole percent or greater and tetrahydrophthalic acid oranhydride at 25 mole percent or greater. All mole percentages are basedupon the total moles of diacid or diol residues.

By contrast, some examples of compositions that would be included in theabove embodiment are those, for example, in which the aliphaticpolyester consists essentially of (i) diacid residues consistingessentially of about 50 to about 85 mole percent of the residues of atleast one cycloaliphatic dicarboxylic acid chosen from1,4-cyclohexanedicarboxylic acid, hexahydrophthalic anhydride, and about50 to about 15 mole percent of the residues at least one acyclicaliphatic dicarboxylic acid chosen from adipic acid, dodecanedioic acid,sebacic acid, azelaic acid, maleic acid, fumaric acid, succinic acid,and glutaric acid; and (ii) diol residues consisting essentially ofabout 75 to 100 mole percent of the residues of2,2,4,4-tetramethyl-1,3-cyclobutanediol and about 25 to 0 mole percentof the residues of at least one diol chosen from neopentyl glycol,ethylene glycol, propylene glycol, diethylene glycol, triethyleneglycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol,heptaethylene glycol, octaethylene glycol, nonaethylene glycol,decaethylene glycol, 1,3-propanediol,2,4-dimethyl-2-ethyl-hexane-1,3-diol, 2,2-dimethyl-1,2-propanediol,2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol,1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol,2,2,4-trimethyl-1,6-hexanediol, thiodiethanol,1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol,1,4-cyclohexanedimethanol, 2,2,4-trimethyl 1,3-pentanediol,hydroxypivalyl hydroxypivalate, 1,10-decanediol, and hydrogenatedbisphenol A. In another example, the curable aliphatic polyesterconsists essentially of (i) diacid residues consisting essentially ofabout 50 to about 85 mole percent of the residues of1,4-cyclohexanedicarboxylic acid, hexahydrophthalic anhydride, or amixture thereof, and about 15 to about 50 mole percent of the residuesof adipic acid; and (ii) diol residues consisting essentially of about75 to 100 mole percent of the residues of TMCD and about 25 to 0 molepercent of the residues of neopentyl glycol. In yet another example, thecurable, aliphatic polyester can consist essentially of (i) diacidresides consisting essentially of about 50 mole percent of the residuesof hexahydrophthalic anhydride and about 50 mole percent of the residuesof adipic acid; and (ii) diol residues consisting essentially of about75 to 100 mole percent of the residues of2,2,4,4-tetramethyl-1,3-cyclobutanediol, and about 25 to 0 mole percentof the residues of neopentyl glycol.

The curable, aliphatic polyester has a glass transition temperature(abbreviated herein as “Tg”) of about −35 to about 35° C. Someadditional, representative examples of Tg ranges for the curable,aliphatic polyester are about −35 to about 30° C., about −35 to about25° C., about −35 to less than 20, about −35 to about 19° C., about −35to about 18° C., about −35 to about 17° C., about −35 to about 16° C.,about −35 to about 15° C., about −35 to about 10° C.

The curable, aliphatic polyester can be prepared by heating thereactants until the desired molecular weight, acid number, or hydroxylnumber is reached. The reaction can be monitored by the collection ofwater (when diacids are used as starting materials) or alcohol (whendiesters are used). The polyester typically can be prepared at atemperature range of about 150 to about 250° C. and at atmosphericpressure or under vacuum. In one embodiment, for example, the diacid anddiol components of the polyester may be partially reacted before thepolyol is added. Once the polyol is added to the reaction mixture,heating is continued until a target acid number is satisfied.

Alternatively, the curable, aliphatic polyester can be prepared in thepresence of a process solvent to help remove the water or alcoholby-products of the reaction and to promote the synthesis of thepolyester resin. The process solvent may be any solvent known in the artas useful for the preparation of polyester polymers. For example, theprocess solvent can be a hydrocarbon solvent. In another example, theprocess solvent can comprise an aromatic hydrocarbon such as, forexample, xylene. The xylene can be a pure isomer, or a mixture of ortho,meta, and para isomers. The amount of process solvent may be determinedby routine experimentation as understood by those skilled in the art.The process solvent can be added in amounts ranging from 0.5 to about 5weight percent, based on the total weight of reaction mixture.

Optionally, a catalyst may be used to promote the synthesis of thepolyester. The catalyst may be any catalyst known in the art to beuseful for the formation of polyester resins. For example, the catalystcan be a tin catalyst, such as, for example, FASCAT™ 4100 (availablefrom Arkema Corporation). The catalyst increases the rate of thepolyester resin reaction, as described above, and its amount may bedetermined by routine experimentation as understood by those skilled inthe art. Ordinarily, the catalyst is added in amounts ranging from about0.01 to about 1.00 weight percent based on the total weight of thereactants.

Our invention also provides a coating composition comprising the variousembodiments of the curable, aliphatic polyester resin containing2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) as described above. Thus,another aspect of the present invention is a thermosetting coatingcomposition, comprising:

-   (A). about 50 to about 90 weight percent, based on the total weight    of (A) and (B) of at least one curable, aliphatic polyester,    comprising    -   i. diacid residues, comprising at least 90 mole percent, based        on the total moles of diacid residues, of the residues of at        least one aliphatic diacid, the aliphatic dicarboxylic acid        comprising about 50 to 100 mole percent of a cycloaliphatic        dicarboxylic acid;    -   ii. diol residues, comprising about 50 to 100 mole percent,        based on the total moles of diol residues, of the residues of        2,2,4,4-tetramethyl-1,3-cyclobutanediol; and    -   iii. about 2 to about 40 mole percent of the residues of at        least one polyol, based on the total moles of diol and polyol        residues;    -   wherein the curable, aliphatic polyester has a number average        molecular weight of about 300 to about 10,000 daltons, a glass        transition temperature of about −35° C. to about 35° C., a        hydroxyl number of about 20 to about 450 mg KOH/g of polyester,        and an acid number of 0 to about 80 mg KOH/g of polyester;-   (B). about 10 to about 50 weight percent, based on the total weight    of (A) and (B) of a crosslinker comprising at least one compound    reactive with a carboxylic acid or a hydroxyl group;-   (C). about 10 to about 60 weight percent, based on the total weight    of (A), (B), and (C) of at least one nonaqueous solvent.

It is understood that the curable, aliphatic polyester component ofcoating composition may include any combination of the variousembodiments of diacids, diols, polyols, acid and hydroxyl numbers, andglass transition temperatures described hereinabove in accordance withthe present invention. For example, the curable, aliphatic polyester cancomprise about 50 mole percent of the residues of1,4-cyclohexanedicarboxylic acid and about 50 mole percent of theresidues of adipic acid, based on the total moles of diacid residues. Inanother example, the curable, aliphatic polyester can contain about 50mole percent of the residues of hexahydrophthalic anhydride and about 50mole percent of the residues of adipic acid. Some additional,non-limiting examples of the diacid component of curable, aliphaticpolyester are as follows: (a) about 50 to about 85 mole percent of theresidues of at least one diacid chosen from 1,4-cyclohexanedicarboxylicacid, 1,3-cyclohexanedicarboxylic acid, hexahydrophthalic anhydride, andcombinations thereof; and about 15 to about 50 mole percent of theresidues of at least one alicyclic aliphatic diacid having from 4 to 10carbon atoms; (b) about 50 to about 85 mole percent of the residues ofat least one diacid chosen from 1,4-cyclohexanedicarboxylic acid,hexahydrophthalic anhydride, and combinations thereof; and about 15 toabout 50 mole percent of the residues of at least one diacid chosen fromadipic acid, succinic acid, and glutaric acid; (c) about 50 to about 75mole percent of the residues of one or diacids chosen from1,4-cyclohexanedicarboxylic acid, hexahydrophthalic anhydride, andcombinations thereof; and about 25 to about 50 mole percent of theresidues of at least one diacid chosen from adipic acid, succinic acid,and glutaric acid; (d) about 50 to about 65 mole percent of the residuesof one or diacids chosen from 1,4-cyclohexanedicarboxylic acid,hexahydrophthalic anhydride, and combinations thereof; and about 35 toabout 50 mole percent of the residues of at least one diacid chosen fromadipic acid, succinic acid, and glutaric acid; (e) about 50 mole percentof the residues of one or diacids chosen from1,4-cyclohexanedicarboxylic acid, hexahydrophthalic anhydride, andcombinations thereof; and about 50 mole percent of the residues ofadipic acid; and (f) about 50 mole percent of the residues of1,4-cyclohexanedicarboxylic acid and about 50 mole percent of theresidues of adipic acid. In addition to the residues of alicyclic andcyclic aliphatic dicarboxylic acids described above, the diacid residuesmay further comprise from 0 to about 10 mole percent of the residues ofat least one aromatic dicarboxylic acid chosen from phthalic acid,terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid,and combinations thereof.

As described previously, the acid component of our inventive polyestercomposition may further comprise the residues of a monocarboxylic acidor a polybasic acid containing more that 2 carboxylic acid groups, suchas, for example, the residues of at least one monobasic or polybasiccarboxylic acid chosen from benzoic acid, acetic acid, 2-ethylhexanoicacid, propionic acid, tert-butyl benzoic acid, butanoic acid;trimellitic acid; 1,2,4-cyclohexanetricarboxylic acid,1,3,4-butanetricarboxylic acid, and 1,2,5-hexanetricarboxylic acid.

In addition to TMCD, the curable, aliphatic polyester of the coatingcomposition can comprise from 0 to about 50 mole percent of at least onealiphatic diol. Representative examples of aliphatic diols include, butare not limited to, neopentyl glycol, ethylene glycol, propylene glycol,diethylene glycol, triethylene glycol, tetraethylene glycol,pentaethylene glycol, hexaethylene glycol, heptaethylene glycol,octaethylene glycol, nonaethylene glycol, decaethylene glycol,1,3-propanediol, 2,4-dimethyl-2-ethyl-hexane-1,3-diol,2,2-dimethyl-1,2-propanediol, 2-ethyl-2-butyl-1,3-propanediol,2-ethyl-2-isobutyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol,1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-ethyl-1,3-hexanediol,2,2,4,4-tetramethyl-1,6-hexanediol, thiodiethanol,1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol,1,4-cyclohexanedimethanol, 2,2,4-trimethyl 1,3-pentanediol,2,4-diethyl-1,5-pentanediol, hydroxypivalyl hydroxypivalate,1,10-decanediol and hydrogenated bisphenol A. For example, in oneembodiment, the curable, aliphatic polyester resins comprise acombination of the residues or neopentyl glycol and TMCD. It should beunderstood that the diols listed above may be used in any combinationwith TMCD and the diacid components and in any amount within the rangesdescribed hereinabove.

For example, in one embodiment, the curable, aliphatic polyester cancomprise (i) diacid residues comprising about 50 to about 85 molepercent of the residues of at least one cycloaliphatic dicarboxylic acidchosen from 1,4-cyclohexanedicarboxylic acid,1,3-cyclohexanedicarboxylic acid, hexahydrophthalic anhydride, and about15 to about 50 mole percent of the residues at least one acylicaliphatic dicarboxylic acid chosen from adipic acid, dodecanedioic acid,sebacic acid, azelaic acid, maleic acid, fumaric acid, succinic acid,and glutaric acid; and (ii) diol residues comprising about 50 to 100mole percent of the residues of TMCD and about 50 to 0 mole percent ofthe residues of at least one diol chosen from neopentyl glycol, ethyleneglycol, propylene glycol, diethylene glycol, triethylene glycol,tetraethylene glycol, pentaethylene glycol, hexaethylene glycol,heptaethylene glycol, octaethylene glycol, nonaethylene glycol,decaethylene glycol, 1,3-propanediol,2,4-dimethyl-2-ethyl-hexane-1,3-diol, 2,2-dimethyl-1,2-propanediol,2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol,1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol,2,2,4-trimethyl-1,6-hexanediol, thiodiethanol,1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol,1,4-cyclohexanedimethanol, 2,2,4-trimethyl 1,3-pentanediol,p-xylenediol, hydroxypivalyl hydroxypivalate, 1,10-decanediol, andhydrogenated bisphenol A. In another example, the curable aliphaticpolyester can comprise (i) diacid residues comprising about 50 to about85 mole percent of the residues of 1,4-cyclohexanedicarboxylic acid,hexahydrophthalic anhydride, or a mixture thereof, and about 15 to about50 mole percent of the residues of adipic acid; and (ii) diol residuescomprising about 50 to 100 mole percent of the residues of TMCD andabout 50 to 0 mole percent of the residues of neopentyl glycol. In yetanother example, the curable, aliphatic polyester can comprise (i)diacid resides comprising about 50 mole percent of the residues ofhexahydrophthalic anhydride and about 50 mole percent of the residues ofadipic acid; and (ii) diol residues comprising about 75 to 100 molepercent of the residues of 2,2,4,4-tetramethyl-1,3-cyclobutanediol, andabout 25 to 0 mole percent of the residues of neopentyl glycol.

In addition to diacid and diol residues, the curable, aliphaticpolyester of the coating composition comprises about 2 to about 40 molepercent of the residues of at least one polyol, based on the total molesof diol and polyol residues. These polyols may include aliphatic,alicyclic, and cyclic alkyl polyols. Some specific examples of polyolsinclude, but are not limited to, trimethylolpropane (abbreviated hereinas “TMP), pentaerythritol (abbreviated herein as “PE”),trimethylolethane (abbreviated herein as “TME”), erythritol, threitol,dipentaerythritol, sorbitol, glycerine, and the like. In one example,the curable, aliphatic polyester can comprise about 3 to about 30 molepercent of the residues of at least one polyol selected fromtrimethylolpropane, pentaerythritol, trimethylolethane, erythritol,threitol, dipentaerythritol, sorbitol, and glycerine. In anotherembodiment, the curable, aliphatic polyester comprisestrimethylolpropane.

The curable, aliphatic polyester of this invention has a hydroxyl numberof about 20 to about 450 mg KOH/g resin. Further examples of hydroxylnumber are about 25 to about 300, and about 30 to about 250. Inaddition, the curable, aliphatic polyester has an acid number of about 0to about 80 mg KOH/g polyester or, in other examples, about 2 to about25 mg KOH/g polyester, and about 2 to about 15 mg KOH/g polyester. Thenumber average molecular weight of the curable, aliphatic polyester isabout 300 daltons to 10000 daltons. Additional examples of molecularweight ranges are about 400 to about 7000, and about 500 to about 5000.The curable, aliphatic polyester has a glass transition temperature(abbreviated herein as “Tg”) of about −35 to about 35° C. Someadditional, representative examples of Tg ranges for the curable,aliphatic polyester are about −35 to about 30° C., about −35 to about25° C., about −35 to less than 20, about −35 to about 19° C., about −35to about 18° C., about −35 to about 17° C., about −35 to about 16° C.,about −35 to about 15° C., about −35 to about 10° C. For example, thecurable, aliphatic polyester can have a hydroxyl number of about 30 toabout 250 mg potassium hydroxide per gram of polyester, an acid numberof about 2 to about 15 mg potassium hydroxide per gram of polyester, anda number average molecular weight of about 700 to about 7000 daltons,and a Tg of about −20 to about 20° C.

The curable, aliphatic polyester resin comprises a reactive functionalgroup, typically a hydroxyl group or carboxyl group for the purpose oflater reacting with a crosslinker in a coating formulation. Thefunctional group is controlled by having either excess diol or acid(from dicarboxylic acid or tricarboxylic acid) in the polyester resincomposition. The desired crosslinking pathway will determine whether thepolyester resin will be hydroxyl-terminated or carboxylicacid-terminated. The concept is known to those skilled in the art anddescribed in Organic Coatings Science and Technology, 2nd ed., p.246-257, by Z. Wicks, F. Jones, and S. Pappas, Wiley, New York, 1999.

The thermosetting coating composition may further contain about 10 toabout 50 weight percent of at least one crosslinker, based on thecombined weight of the polyester and the crosslinker. Typically, thecrosslinker will be a compound, generally known in the art, that canreact with either the carboxylic acid-terminated or hydroxyl-terminatedpolyester resin. For example, the crosslinker can comprise at least onecompound chosen from epoxides, melamines, hydroxy alkyl amides, andisocyanates. For example, epoxide crosslinkers will react with acarboxylic acid-terminated polyester resin, whereas melamines,isocyanates, and isocyanurates will react with a hydroxyl-terminatedpolyesters.

Melamine or “amino” crosslinkers also are well-known in the art and canbe used in the coating composition of the invention. For example, thecoating composition of the present invention can comprise at least onemelamine compound chosen from hexamethoxymethylmelamine,tetramethoxymethylbenzoguanamine, tetramethoxy-methylurea, and mixedbutoxy/methoxy substituted melamines. Some examples of commerciallyavailable melamine crosslinkers include the CYMEL™ 300 series and CYMEL™1100 series melamine crosslinkers, available from Cytec SurfaceSpecialties. The polyester to melamine weight ratio is typically about50:50 to about 90:10. Other examples of polyester:melamine weight ratiosare about 60:40 to about 85:15 and about 65:35 to about 80:20.

In addition to melamines, isocyanates and isocyanurates can be used ascrosslinkers in accordance with the invention. Representativeisocyanates and isocyanurates include, but are not limited to, toluenediisocyanate, isocyanurates of toluene diisocyanate, diphenylmethane4,4′-diisocyanate, isocyanurates of 4,4′-diisocyanate,methylenebis-4,4′-isocyanatocyclohexane, isophorone diisocyanate,isocyanurates of isophorone diisocyanate, the biuret of1,6-hexamethylene diisocyanate, 1,6-hexamethylene diisocyanate,isocyanurates of 1,6-hexamethylene diisocyanate, 1,4-cyclohexanediisocyanate, p-phenylene diisocyanate, and triphenylmethane4,4′,4″-triisocyanate, tetramethyl xylene diisocyanate, metaxylenediisocyanate, polyisocyanates, 1,4-butylene diisocyanate, methylenebis(4-cyclohexyl isocyanate), isophorone diisocyanate andisocyanate-terminated adducts of ethylene glycol, 1,4-butylene glycol,trimethylol propane, or combinations thereof.

The coating composition also can comprise isocyanate-terminated adductsof diols and polyols, such as ethylene glycol, 1,4-butylene glycol,trimethylol propane, etc., as crosslinkers. These crosslinkers areformed by reacting more than one equivalent of a diisocyanate, such asthose mentioned above, with one equivalent of a diol or polyol to form ahigher molecular weight isocyanate prepolymer with a isocyanatefunctionality of 2 to 3. Some commercial examples ofisocyanate-terminated adducts include isocyanate crosslinkers under theDESMODUR™ and MONDUR™ trademarks available from Bayer Material Scienceand under the TOLONATE™ trademark from Perstorp Corporation.

In one embodiment of the invention, the crosslinker comprises at leastone aliphatic isocyanate, which can provide good outdoor durability andcolor stability in the cured coating. Examples of aliphatic isocyanatesinclude 1,6-hexamethylene diisocyanate, 1,4-butylene diisocyanate,methylene bis(4-cyclohexyl isocyanate), isophorone diisocyanate, andcombinations thereof. Mixtures of isocyanate crosslinkers can also beemployed. In yet another embodiment, the crosslinker can compriseisocyanurates of 1,6-hexamethylene diisocyanate, the biuret of1,6-hexamethylene diisocyanate, or a mixture thereof.

Stoichiometric calculations for the curable, aliphatic polyester andisocyanate reaction are known to those skilled in the art and aredescribed in The Chemistry of Polyurethane Coatings, TechnicalPublication, p. 20, by Bayer Material Science, 2005. Persons havingordinary skill in the art will understand that crosslinking between thepolyester resin and isocyanate reaches maximum molecular weight andoptimal properties associated with molecular weight at anisocyanate:hydroxyl equivalent ratio of about 1:1; that is, when oneequivalent of isocyanate (—NCO) reacts with one equivalent of hydroxyl(—OH). Typically, however, a small excess of isocyanate, for example,about 5 to about 10% above a 1:1 equivalent, is used to allow for theloss of isocyanate by the reaction with adventitious moisture from theatmosphere, solvents, and pigments. Other NCO:OH ratios can be used; forexample, it may be desirable to vary the NCO to OH ratio to less than1:1 to improve flexibility or greater than 1:1 to produce harder, morechemical resistant, and more weather resistant coatings.

For the present invention, the solvent borne, thermosetting coatingcomposition has an NCO:OH ratio, on an equivalent basis, of about0.9:1.0 to about 1.5:1.0. Examples of other NCO:OH ratios are about0.95:1.0 to about 1.25:1.0 and about 0.95:1.0 to about 1.1:1.0.

The thermosetting coating composition also comprises about 10 to about60 weight percent, based on the total weight of components (A), (B), and(C) of a solvent. Examples of solvents include, but are not limited to,benzene, xylene, mineral spirits, naptha, toluene, acetone, methyl ethylketone, methyl n-amyl ketone, methyl isoamyl ketone, n-butyl acetate,isobutyl acetate, t-butyl acetate, n-propyl acetate, isopropyl acetate,ethyl acetate, methyl acetate, ethanol, n-propanol, isopropanol,n-butanol, sec-butanol, isobutanol, ethylene glycol monobutyl ether,propylene glycol n-butyl ether, propylene glycol methyl ether, propyleneglycol monopropyl ether, dipropylene glycol methyl ether, diethyleneglycol monobutyl ether, trimethylpentanediol mono-isobutyrate, ethyleneglycol mono-octyl ether, diacetone alcohol,2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (available commerciallyfrom Eastman Chemical Co. under the trademark TEXANOL™), or combinationsthereof. The coating composition may also comprise reactive solventssuch as, for example, diallyl phthalate, SANTOLINK™ XI-100 polyglycidylallyl ether (available from Cytec), and others as described, forexample, in U.S. Pat. Nos. 5,349,026 and 5,371,148.

The coating composition, optionally, can further comprise at least onecrosslinking catalyst. Representative crosslinking catalysts includecarboxylic acids, sulfonic acids, tertiary amines, tertiary phosphines,tin compounds, or combinations of these compounds. Some specificexamples of crosslinking catalysts are at least one compound chosen fromp-toluenesulfonic acid, dodecylbenzene sulfonic acid, dinonylnaphthalenesulfonic acid, and dinonylnaphthalene disulfonic acid, benzoic acid,triphenylphosphine, dibutyltindilaurate, and dibutyltindiacetate. Theselection of a crosslinking catalyst typically depends on the type ofcrosslinker that is used in the coating composition. For example, thecrosslinker can comprise a melamine or “amino” crosslinker and thecrosslinking catalyst can comprise p-toluenesulfonic acid, unblocked andblocked dodecylbenzene sulfonic (abbreviated herein as “DDBSA”),dinonylnaphthalene sulfonic acid (abbreviated herein as “DNNSA”) anddinonylnaphthalene disulfonic acid (abbreviated herein as “DNNDSA”).Some of these catalysts are available commercially under the trademarkssuch as, for example, NACURE™ 155, 5076, 1051, and 5225 (available fromKing Industries), BYK-CATALYSTS™ (available from BYK-Chemie USA), andCYCAT™ catalysts (available from Cytec Surface Specialties).

In another embodiment, the curable, aliphatic polyester can comprisehydroxyl-terminated end groups and the crosslinker can comprise anisocyanate. The coating composition also can comprise at least oneisocyanate crosslinking catalyst such as, for example, FASCAT™ 4202(dibutyltindilaurate), FASCAT™ 4200 (dibutyltindiacetate, both availablefrom Arkema), DABCO™ T-12 (available from Air Products) and K-KAT™ 348,4205, 5218, XC-6212™ non-tin catalysts (available from King Industries),and tertiary amines.

In another example, the thermosetting coating composition can compriseabout 25 to about 35 weight percent solvent, about 20 to about 35 weightpercent of a melamine crosslinker, and a crosslinking catalystcomprising p-toluenesulfonic acid. In another example, the thermosettingcoating composition comprises about 25 to about 35 weight percentsolvent and about 20 to about 35 weight percenthexamethoxy-1-methylmelamine.

The coating composition of the instant invention may further contain atleast one coating additive known in the art. Examples of coatingadditives include, but are not limited to, leveling, rheology and flowcontrol agents such as silicones, fluorocarbons or cellulosics;extenders; plasticizers; flatting agents; pigment wetting and dispersingagents; ultraviolet (UV) absorbers; UV light stabilizers; defoaming andantifoaming agents; anti-settling, anti-sag and bodying agents;anti-skinning agents; anti-flooding and anti-floating agents; andcorrosion inhibitors. Specific examples of such additives can be foundin the Raw Material Index and Buyer's Guide, published by the NationalPaint & Coatings Association, 1500 Rhode Island Avenue, N.W.,Washington., DC 20005. Further examples of such additives may be foundin U.S. Pat. No. 5,371,148.

Examples of flatting agents include, but are not limited to, syntheticsilica, available from the Davison Chemical Division of W. R. Grace &Company as SYLOID™; polypropylene, available from Hercules Inc., asHERCOFLAT™; and synthetic silicate, available from J. M. HuberCorporation, as ZEOLEX™. Examples of dispersing agents include, but arenot limited to, sodium bis(tridecyl) sulfosuccinate, di(2-ethyl hexyl)sodium sulfosuccinate, sodium dihexylsulfosuccinate, sodium dicyclohexylsulfosuccinate, diamyl sodium sulfosuccinate, sodium dusobutylsulfosuccinate, disodium isodecyl sulfosuccinate, disodium ethoxylatedalcohol half ester of sulfosuccinic acid, disodium alkyl amidopolyethoxy sulfosuccinate, tetra-sodiumN-(1,2-dicarboxyethyl)-N-octadecyl sulfosuccinamate, disodiumN-octasulfosuccinamate, sulfated ethoxylated nonylphenol,2-amino-2-methyl-1-propanol, and the like.

Examples of viscosity, suspension, and flow control agents include, butare not limited to, polyaminoamide phosphate, high molecular weightcarboxylic acid salts of polyamine amides, and alkylene amine salts ofan unsaturated fatty acid, all available from BYK Chemie USA as ANTITERRA™. Further examples include, but are not limited to, polysiloxanecopolymers, polyacrylate solution, cellulose esters, hydroxyethylcellulose, hydroxypropyl cellulose, polyamide wax, polyolefin wax,hydroxypropyl methyl cellulose, polyethylene oxide, and the like.

Several proprietary antifoaming agents are commercially available andinclude, but are not limited to, BUBREAK™, available from BuckmanLaboratories Inc., BYK™, available from BYK Chemie, U.S.A., FOAMASTER™and NOPCO™, available from Henkel Corp./Coating Chemicals, DREWPLUS™,available from the Drew Industrial Division of Ashland Chemical Company,TROYSOL™ and TROYKYD™, available from Troy Chemical Corporation, andSAG™, available from Union Carbide Corporation.

Examples of UV absorbers, UV light stabilizers, and antioxidantsinclude, but are not limited to, substituted benzophenone, substitutedbenzotriazoles, hindered amines, hindered benzoates, phenols, andphosphites, some of which are available from Cytec Specialty Chemicalsas CYASORB® UV, and from Ciba Specialty Chemicals as TINUVIN®,CHIMASSORB®, IRGANOX® and IRGAFOS®;diethyl-3-acetyl-4-hydroxy-benzyl-phosphonate, 4-dodecyloxy-2-hydroxybenzophenone, and resorcinol monobenzoate. For example, in oneembodiment, the thermosetting coating composition can contain IRGANOX®1010 antioxidant, available from Ciba Specialty Chemicals.

Such paint or coating additives as described above form a relativelyminor proportion of the coating composition, generally about 0.05 weightpercent to about 5.00 weight percent. For example, a coating compositionoptionally may contain at least one of the above-described additives andat least one pigment.

The solvent borne thermosetting coating composition, as described above,also may comprise at least one pigment. Typically, the pigment ispresent in an amount of about 20 to about 60 weight percent, based onthe total weight of the composition. Examples of pigments include thosegenerally recognized by persons of ordinary skill in the art of surfacecoatings. For example, the pigment may be a typical organic or inorganicpigment, especially those set forth by the Colour Index, 3rd ed., 2ndRev., 1982, published by the Society of Dyers and Colourists inassociation with the American Association of Textile Chemists andColorists. Other examples of suitable pigments include, but are notlimited to, titanium dioxide, barytes, clay, calcium carbonate, CIPigment White 6 (titanium dioxide), CI Pigment Red 101 (red iron oxide),CI Pigment Yellow 42, CI Pigment Blue 15, 15:1,15:2, 15:3,15:4 (copperphthalocyanines); CI Pigment Red 49:1 and CI Pigment Red 57:1. Colorantssuch as, for example, phthalocyanine blue, molybdate orange, or carbonblack also may be added to the coating composition. For example, thesolvent borne, thermosetting coating formulations can contain titaniumdioxide as the pigment.

The thermosetting coating composition of this invention may optionallycomprise a TSA resin. Thermosetting acrylic (“TSA”) resins are preparedby free radical polymerization in bulk or in a solvent. Initiators areof the free radical type and are usually organic peroxides or azocompounds, such as benzoyl peroxide, t-butyl hydroperoxide, t-butylperoxide, t-butyl peroxybenzoate, azobisisobutyronitrile, and2,2′-azobis(2,4-dimethyl)-valeronitrile. The reaction is preferablycarried out at the reflux temperature of the solvent used, which isgenerally higher than the thermal decomposition temperature of theinitiator employed. The acrylic resin is composed of ethylenicallyunsaturated monomers that include acrylate, methacrylate, styrene,(meth) acrylic acid, and vinyl esters. They further contain hydroxyl,epoxy, carboxyl, blocked-phenol and/or acetoacetoxy functional groups.Suitable examples of preparation methods and components of the acrylicresin include those known in the art including, but not limited to,those described above, and in Resins for Surface Coatings, Vol. II, p.121-210, ed. by P. K. T. Oldring and G. Hayward, SITA Technology,London, UK, 1987.

Examples of hydroxyl functional TSA resins include the MACRYNAL™ series,available from Cytec Surface Specialties; the ACRYLOID™ series,available from Rohm and Haas; and the JONCRYL™ series, available fromBASF Corporation. One specific example of a hydroxyl functional TSAresin used is MACRYNAL™ SM 515/70BAC, available from Cytec SurfaceSpecialties.

The curable, aliphatic polyester and the TSA resin can be blendedtogether. The weight percent of polyester in the blend is about 5 toabout 50 wt. percent preferably about 10 to about 40 weight percent, andmost preferably about 15 to about 30 weight percent.

Typically, the thermosetting coating composition and additives can beformulated into coating that contains about 40 to about 90%non-volatiles. After formulation, the coating composition can be appliedto a substrate or article. Thus, a further aspect of the presentinvention is a shaped or formed article that has been coated with thecoating compositions of the present invention. The substrate can be anycommon substrate such as paper; polymer films such as polyethylene orpolypropylene; wood; metals such as aluminum, steel or galvanizedsheeting; glass; urethane elastomers; primed (painted) substrates; andthe like. The coating composition can be coated onto a substrate usingtechniques known in the art, for example, by spraying, draw-down,roll-coating, etc., about 0.5 to about 4 mils of wet coating onto asubstrate. The coating can be cured at ambient (room) temperature orheated in a forced air oven to a temperature of about 50° C. to about175° C., for a time period that typically ranges about 5 to about 90minutes and allowed to cool. Further examples of typical application andcuring methods can be found in U.S. Pat. Nos. 4,737,551 and 4,698,391and 3,345,313. The invention is further illustrated by the followingexamples.

EXAMPLES Preparation of Curable, Aliphatic Polyesters ComparativeExample P1, Example P2, Example P3 and Example P4

The example and comparative aliphatic polyester resins (Table 1) wereprepared according to the following procedure, targeting a numberaverage molecular weight=1250, a hydroxyl equivalent weight=500, ahydroxyl functionality=2.5 and final acid number=8.

The resins were prepared using a solvent process to help remove thewater of esterification. The resins were prepared in a two-literreaction kettle equipped with a heating mantle, mechanical stirrer,thermocouple, nitrogen blanket (0.6 scfh), oil-heated partial condenser(103° C.-105° C.), condensate trap, and water-cooled total condenser(15° C.). The condensate trap, kettle top and adapter from the kettle tothe column were insulated by aluminum foil and fiberglass tape tofacilitate water removal. Stage 1 raw materials were charged to thereactor. Additional xylene (approximately 30 g) was used to fill thecondensate trap. The temperature was then increased from roomtemperature to 150° C. over ninety minutes to form a homogenous melt.Agitation (300 rpm) was started and the temperature increased to amaximum of 230° C. over 240 minutes. The Stage 2 TMP was added when halfthe theoretical condensate was collected. The reaction mixture was heldat 230° C. until a final acid number of 6±2 mg KOH/g resin was obtained.The resins were then poured into a metal paint can.

The acid number (abbreviated “AN”), hydroxyl number (abbreviated “OH#”),number average molecular weight (abbreviated “Mn”) and glass transitiontemperature (abbreviated “Tg”) of the polyesters are shown in Table 1.Acid number was determined using ASTM method D 1639. Hydroxyl number wasdetermined by esterifying the resin by reaction with excess aceticanhydride in pyridine and then decomposing the unreacted anhydride withwater. The resulting acetic acid is then titrated with a standardsolution of KOH. The number of milligrams KOH which are equivalent toone gram of resin sample is reported as the hydroxyl number. Numberaverage molecular weight was determined by gel permeation chromatographyusing a refractive index detector with polystyrene standards.

Residual xylene remaining in the resin from solvent processing couldartificially lower the Tg measurement. To obtain a more accurate Tg, aresin sample was first subjected to preconditioning in a TGA (thermalgravimetric analysis) instrument. It was placed into a stainless steelDSC pan and heated under nitrogen atmosphere from room temperature to150° C. at a rate of 5° C./min. The sample was then transferred to adifferential scanning calorimeter with modulating capability (TAInstruments Q2000 MDSC with Universal software V4.3A). On the firstheating cycle, the sample was heated under nitrogen atmosphere from−120° C. to 125° C. at a rate of 5° C./min. modulating at ±0.796°C./min. Next, it was cooled to −120° C. at 5° C./min. modulating at±0.796° C./min. For the second heating cycle, the sample was heatedunder the same conditions as those used in the first heating cycle. Themidpoint of the second heating cycle is reported as the Tg of thesample.

Each resin was reduced to 70 weight percent solids in n-butyl acetate(n-BuOAc). The solutions were then evaluated for color, clarity andsolution viscosity. Platinum-Cobalt color was measured with a GardcoLICO 100 colorimeter in accordance with ASTM method D 1209. Color valuesranging from 0 to 100 are colorless to very slight yellow color,respectively.

Clarity of the solutions was measured with a BYK-Gardner haze-guard plusinstrument according to ASTM method D 1003, Method A, and is reported aspercent haze.

Solution viscosity was determined using a Brookfield Model LV DV II+ Proviscometer. Viscosity was measured in a 4 oz. jar at 100 rpm usingspindle #63. Viscosity readings below 1000 centipoise are considered tobe very low.

As shown in Table 1, polyesters P2, P3, and P4 have low color, goodclarity and low viscosity. All are suitable for blending with a TSAresin and formulating into a high solids, solvent borne thermosettingcoating.

TABLE 1 Polyester Resin Charge Weights (Grams) and Determined ResinProperties Comparative Polyester Formulation Example P1 Example P2Example P3 Example P4 Mole % TMCD in Polyester 0 75 100 100 Stage 1NPG^((a), (b)) 435.38 95.84 — — TMCD^((a), (c)) — 398.10 510.45 510.47TMP^((d)) 35.91 36.53 36.71 36.71 AD^((e)) 293.41 258.28 248.36 248.37CHDA^((g)) 345.69 304.31 292.62 HHPA^((h)) — — — 262.02 Fascat 4100catalyst^((f)) 1.14 1.12 1.12 1.09 Xylene process solvent 22.84 22.4822.40 21.78 Stage 2 TMP 35.91 36.53 36.71 36.71 Total Charge 1170.281153.19 1148.37 1117.15 Minus Theo. Condensate 142.00 124.70 119.8189.22 Yield 1028.28 1028.49 1028.56 1027.93 Determined Resin PropertiesAN (mg KOH/g resin) 5 8 5 4 OH# (mg KOH/g resin) 103 103 94 92 M_(n)(daltons) 1959 1937 2106 2182 T_(g) (° C.) −27.7 −6.7 1.3 7.8 ResinProperties at 70 wt. % in n- BuOAc Platinum-Cobalt Color 0 1 11 55Clarity (% Haze) 0.83 0.53 0.98 1.55 Viscosity, cP 339 380 894 760^((a))Includes a glycol excess of 1 wt. % based on calculated chargeweights ^((b))2,2-Dimethyl-1,3-propanediol (Eastman)^((c))2,2,4,4-tetramethy1-1,3-cyclobutanediol (Eastman)^((d))Trimethylolpropane (Perstorp) ^((e))Adipic acid (DuPont)^((f))Butylstannoic acid (Arkema) ^((g))1,4-Cyclohexanedicarboxylic acid^((h))Hexahydrophthalic anhydride

Preparation of TSA/Aliphatic Polyester Blends

Examples B3, B4, B5, B7, B8, B9, B11, B12, and B13 illustrate blends ofa TSA with the aliphatic polyesters of the invention, while examples B1,B2, B6, and B10 are comparative examples. The properties of theTSA/aliphatic polyester blends are listed in Table 2.

The aliphatic polyester resins were evaluated for compatibility with acommercially available TSA resin, MACRYNAL™ SM 515/70BAC (available fromCytec Surface Specialties). MACRYNAL™ SM 515 is a hydroxy functionalacrylic that is crosslinkable with aliphatic polyisocyanates. This TSAresin is suggested for use by the manufacturer in air-drying and forceddrying two pack high solids thermosetting coatings.

The TSA/polyester resin blends were evaluated at 70 weight percentsolids in n-butyl acetate at TSA:polyester weight ratios of 85:15, 75:25and 65:35. MACRYNAL™ SM 515 was supplied as a 70 weight percent solutionin n-butyl acetate, and all of the polyester resins were reduced to 70weight percent solids in n-butyl acetate. The appropriate amount ofacrylic and polyester resin solutions were combined in a 4 oz. jar asindicated in Table 2. The solutions were then rolled at room temperaturefor 24 hours to thoroughly mix the components.

The viscosity of the TSA/polyester blends was determined using aBrookfield Model LV DV II+ Pro viscometer. Viscosity was measured in the4 oz. jar at 20 rpm using spindle #63 and is reported in centipoise. Aportion of each TSA/polyester blend was cast as a 10 mil wet film ontoglass and force-dried for 7 hrs. at 80° C. (176° F.) then dried at roomtemperature drying for 4 days before evaluation.

The Tg of the blends was determined on samples of the dried cast filmsusing a differential scanning calorimeter with modulating capability (TAInstruments Q2000 MDSC with Universal software V4.3A). On the firstheating cycle, the sample was heated under helium atmosphere from −120°C. to 125° C. at a rate of 5° C./min. and modulating at ±0.531° C./40sec. The sample then was quench-cooled with liquid nitrogen to −120° C.For the second heating cycle, the sample was heated under the sameconditions as those used in the first heating cycle. The midpoint of thesecond heating cycle is reported as the Tg of the sample.

The compatibility of the aliphatic polyester with the TSA resin wasdetermined by measuring the percent haze of the dried films according toASTM method D 1003, Method A, using a BYK-Gardner HAZE-GARD PLUS™instrument.

Table 2 shows that the viscosity of the TSA resin was lowered whenblended with any of the polyesters. Viscosity decreases as the polyestercontent increases. In addition, comparative examples B2, B6, and B10show the greatest reduction in Tg from the TSA alone, especially as thepolyester content increases. Example blends B3, B4, B5, B7, B8, B9, B11,B12 and B13 have less impact on Tg. The combination of TMCD/HHPA inpolyester P4 exhibits the greatest Tg retention. At 35% polyestercontent, Example blend B13 made from polyester P4 experienced only a 7°C. drop from the original Tg of the TSA versus a 35° C. drop forComparative blend B10 containing polyester P1.

The compatibility of Example polyesters P2, P3 and P4 with the TSA, asindicated by percent haze were similar to blends made from Comparativepolyester P1 and the TSA alone.

TABLE 2 Properties of TSA/Aliphatic Polyester Blends TSA/Polyester 100/085/15 75/25 65/35 Example Blend B1^((a)) B2^((a)) B3 B4 B5 B6^((a)) B7B8 B9 B10^((a)) B11 B12 B13 Mole % TMCD — 0 75 100 100 0 75 100 100 0 75100 100 in Polyester Grams^((b)) Cytec Macrynal SM 100 85 85 85 85 75 7575 75 65 65 65 65 515 TSA Resin Comparative P1 0 15 0 0 0 25 0 0 0 35 00 0 Example P2 0 0 15 0 0 0 25 0 0 0 35 0 0 Example P3 0 0 0 15 0 0 0 250 0 0 35 0 Example P4 0 0 0 0 15 0 0 0 25 0 0 0 35 Properties Viscosityat 2897 1566 1704 2040 1962 1254 1404 1908 1872 1044 1116 1644 1624 70Wt. % Solids, cP T_(g),° C. 37 25 32 33 34 13 25 31 32 2 22 27 30 Haze,% 0.11 0.22 0.14 0.13 0.11 0.38 0.40 0.11 0.18 0.12 0.22 0.26 0.17^((a))Comparative example. ^((b))All resins are 70 wt. % solids inn-BuOAc.

Preparation of Polyurethane Coatings

White-pigmented polyurethane coatings were prepared from aliphaticpolyester resins P1, P3, and P4 and are shown in Table 3. The resinswere crosslinked with the triisocyanurate of 1,6-hexamethylenediisocyanate at a 1.1:1 NCO:OH ratio.

The Part A aliphatic polyester and pigment were added to a 500-mLstainless steel beaker. A cowles disperser was used to grind the resinand pigment to a 7+ Hegman for about 5 min. at 5000 rpm. The flow aidthen was added and thoroughly mixed for a few minutes. Finally, thecatalyst and solvent blend were added and thoroughly mixed. The totalPart A mixture was transferred into a glass jar and rolled until needed.The Part B crosslinker was added to Part A and thoroughly mixed with awooden tongue depressor then filtered through a Hayward PE 100 PN164300M felt paint filter inside a medium mesh paper filter.

Coating viscosity was determined with a Gardco mini Ford dip cup #4. Theinitial viscosity measurement was made after combining and thoroughlymixing Part B with Part A. Viscosity was then measured every two hoursthereafter and is shown in Table 3.

A wire wound rod was used to apply the coating to glass microscopeslides and polished cold rolled steel test panels with Bonderite 1000pretreatment. The rod was selected to achieve a 1.5±0.2 mil dry filmthickness.

The coatings were force-dried 30 minutes at 250° F. (121.1° C.). Withthe exception of König pendulum hardness, all of the coating mechanicalproperties were determined after 21 days ambient aging. Specular gloss,distinctness of image, reflectance, color, hardness, flexibility,solvent resistance, chemical resistance and accelerated weathering (UVAand constant humidity) resistance of the coatings were determined andreported in Tables 4-9.

Dry film thickness (abbreviated “DFT”) was measured with a FischerscopeMMS Multi Measuring System permascope (Fischer Technology) using theprobe for ferrous substrates. Specular gloss was measured with aBYK-Gardner micro-TRI-gloss meter in accordance with ASTM method D 523.Distinctness of image (abbreviated “DOI”) was measured with aBYK-Gardner wave-scan DOI instrument according to ASTM method E 430.

Color (CIE L*a*b*) and reflectance (CIE Y) values were measured with aHunterLab UltraScan PRO spectrophotometer in accordance with ASTM methodE 313. Values were calculated using D65 illuminant and 10-degreeobserver. MEK double rub solvent resistance was performed with a 32 oz.ball peen hammer wrapped in 16 layers of cotton cheesecloth inaccordance with ASTM method D1308. The number passed is reported as thelast rub until any breakthrough of the coating to metal was observed.The test was run to a maximum of 300 double rubs with observations madeon the left, middle and right side of the rubbed path.

Hardness was determined by three methods: a BYK-Gardner pendulumhardness tester using ASTM method D 4366; by pencil test using ASTMmethod D 3363; and with an Instron Wilson-Wolpert Tukon 2100Bindentation hardness tester using ASTM method E 384. For pendulumhardness, the König method (abbreviated “KPH”) is reported. KPH wasfollowed over the course of 21 days. The first measurement, Day 1, wastaken 24 hours after cure at 250° F. For pencil hardness, the valuereported is the last pencil that did not cut through the coating tometal. Tukon hardness was measured on coatings applied to glassmicroscope slides. The instrument was set to run with a 10 g weight and13 second indent time using 20× magnification. Tukon hardness isreported using the Knoop scale (abbreviated “HK”).

Flexibility was measured as impact resistance with a Gardco Model 172universal impact tester in accordance with ASTM method D 2794. Thevalues reported are the last impact to not produce any crack in thecoating film or delamination of the coating from the substrate.

Resistance to a 50% solution of sulfuric acid (H₂SO₄) was performedunder ambient conditions for 36 days and measured according to ASTMmethod D 1308. A drop of the acid solution was placed onto the coating,covered with a watch glass and sealed with paraffin wax. Test areas wererinsed with water before inspecting for blister formation.

To gage outdoor durability, the coatings were subjected to QUVA (340 nm)accelerated weathering using a QUV/SE instrument (Q-Lab). The testcondition for ‘general metal’ coatings per ASTM method D 4587 wasselected that includes 4 hours UV exposure at 60° C. followed by 4 hourscondensation at 50° C. Test panel edges and back were taped to protectagainst rust formation. Measurements were taken 2 hours into the UVlight cycle to ensure a dry surface and consistency of measurement. Testpanels were rotated after each observation interval. The coatings weretested for gloss retention (20° and 60° per ASTM method D 523) and colorchange (Hunter ΔE* and Yellowness Index, ASTM method E 308 and ASTMmethod D 1925). The results are shown in Tables 5 and 6.

The outdoor durability of a coating also was determined by testing itswater resistance using controlled condensation as described in ASTMmethod D 4585. The coatings were placed in a Cleveland condensing typehumidity cabinet (Q-Lab Model QCT/ADO) for continuous 60° C. mistingwith deionized water. The edges and back of the test panels were tapedto protect against rust formation. They were rotated after eachobservation interval. The coatings were evaluated for gloss retention(20° and 60° per ASTM D 523) and degree of blistering (using ASTM methodD 714). The results are shown in Tables 7, 8 and 9.

Table 3 shows that example coatings C2 and C3 show similar pot lives ascomparative example C1 (based on NPG glycol as the diol). Coatingmechanical properties are presented in Table 4.

Examples C2 and C3 exhibit higher gloss, DOI, and reflectance thancomparative example C1. Color is relatively similar for all of thecoatings. Examples C2 and C3 also have a more uniform and brilliantappearance as indicated by the higher gloss, DOI and reflectance values.

MEK double rub solvent resistance was higher across the coating surfacefor examples C2 and C3 than comparative example C1. In particular, thecombination of TMCD/CHDA in example C2 showed no breakthrough of thecoating to the substrate.

Hardness, as measured by pencil, Tukon and Konig pendulum tests, isgreater for examples C2 and C3. In addition, examples C2 and C3 displaysimilar flexibility to comparative example C1. Examples C2 and C3 wereunaffected after 36 days exposure to H₂SO₄ solution, whereas comparativeexample C1 blistered.

After ˜3500 hours QUVA (340 nm) accelerated weathering exposure,examples C2 and C3 had greater gloss retention than comparative exampleC1 (see Table 5). Gloss retention of examples C2 and C3 was about 4.5times longer. Examples C2 and C3 also exhibited a Hunter ΔE* shift andYellow Index shift of only one unit over the entire test period (seeTable 6).

Examples C2 and C3 had greater gloss retention with little or no blisterdevelopment than comparative example C1 when subjected to Clevelandhumidity testing (see Tables 7, 8 and 9). In particular, example C3retained 73% of its original 20° gloss after 10,000 hours exposure withno blister formation.

TABLE 3 Comparative and Example Polyurethane Coating Formulation Weights(Grams) and Pot Life Coating Formulation Comparative Example ExampleExample C1 C2 C3 Polyester Formulation from Example 1 P1 P3 P4 Mole %TMCD in Polyester 0 100 100 Part A-Grind Polyester resin (70 wt. % inn-BuOAc) 76.23 76.23 76.45 Ti-Pure R960 TiO₂ pigment^((a)) 51.89 51.8951.89 Part A-Let Down BYK-300^((b)) (10 wt. % in n-BuOAc) 2.59 2.59 2.59Fascat 4202^((c)) catalyst 0.82 0.82 0.82 (1 wt. % in n-BuOAc) Solventblend (45/45/10 40.99 40.99 40.94 Xylene/MAK/EEP) Total Part A 172.52172.52 172.70 Part B Desmodur N 3390 BA/SN(d) (90 wt. 27.48 27.48 27.30% in 1/1 n-BuOAc/solvent naptha 100) Total Parts A + B 200.00 200.00200.00 Pot Life (Coating Viscosity, sec.) 0 Hours 9.2 11.6 9.9 1 Hour10.0 12.1 10.2 2 Hours 11.1 12.0 10.3 3 Hours — 12.4 — 4 Hours 13.1 12.911.6 5 Hours 14.7 — — 6 Hours 17.8 — 19.4 ^((a))DuPont TitaniumTechnologies. ^((b))BYK-Chemie. ^((c))Arkema (dibutyltindilaurate).^((d))Bayer MaterialScience (aliphatic polyisocyanate HDI trimer).

TABLE 4 Comparative and Example Polyurethane Coating Properties CoatingFormulation Comparative Ex- Ex Example ample ample C1 C2 C3 PolyesterFormulation from Example 1 P1 P3 P4 Mole % TMCD in Polyester 0 100 100Gloss −20° 72 79 81 −60° 87 88 90 DOI 90 93 93 Reflectance (Y-value) 8892 91 Color L*   95.33   96.69   96.23 a*   −1.24   −1.08   −1.11 b*  −0.02   −0.31   −0.41 MEK Dbl Rubs (# passed) Left 285  300+ 273 Middle 300+ 300+ 300+ Right 133  300+ 289  Pencil Hardness 1 H 3 H 3 HTukon Hardness (HK) <1   13.9   15.7 König Pendulum Hardness (sec.) Day1 16 146  157  Day 2 17 157  167  Day 7 17 158  169  Day 14 17 162  171 Day 21 17 161  170  Impact Resistance (in.-lb.) Forward 150  150  174 Reverse 126  84 78 50% H₂SO₄ Resistance Appearance after 36 daysModerate No No blistering. effect. effect.

TABLE 5 QUVA Accelerated Weathering Gloss Retention of Comparative andExample Polyurethane Coatings Coating Formulation Comparative ExampleExample Example C1 C2 C3 Polyester Formulation from Example 1 P1 P3 P4Mole % TMCD in Polyester 0 100 100 Hours Exposure 20° Gloss   0 70.580.4 81.9  250 70.3 78.0 82.8  500 67.9 79.1 82.8  750 14.1 77.8 82.51000 — 71.8 79.5 1250 — 64.5 81.6 1500 — 54.4 68.4 1750 — 43.1 65.1 2000— 37.8 64.1 2244 — 29.9 48.7 2478 — 24.6 37.0 2728 — 18.3 23.3 2978 —17.4 24.4 3228 — 20.0 22.7 3478 — 13.6 11.3 Hours Exposure 60° Gloss   085.9 87.4 90.5  250 86.0 85.5 90.4  500 85.1 86.6 90.2  750 48.9 87.490.7 1000 — 86.6 89.1 1250 — 85.0 89.7 1500 — 81.9 84.2 1750 — 77.2 84.12000 — 75.5 84.2 2244 — 71.9 78.6 2478 — 67.0 71.4 2728 — 61.0 66.1 2978— 61.4 64.1 3228 — 63.8 58.3 3478 — 56.6 51.1

TABLE 6 QUVA Accelerated Weathering Color Change of Comparative andExample Polyurethane Coatings Coating Formulation Comparative ExampleExample Example Cl C2 C3 Polyester Formulation from Example 1 P1 P3 P4Mole % TMCD in Polyester 0 100 100 Hours Exposure ΔE   0 0.0 0.0 0.0 250 0.5 0.2 0.3  500 0.5 0.4 0.2  750 0.4 0.3 0.2 1000 — 0.6 0.4 1250 —0.4 0.3 1500 — 0.8 0.9 1750 — 0.8 0.6 2000 — 0.6 0.5 2244 — 0.7 0.7 2478— 0.8 0.8 2728 — 0.8 0.9 2978 — 1.0 1.0 3228 — 0.9 0.8 3478 — 1.0 0.9Hours Exposure Yellow Index   0 −1.9 −1.8 −1.9  250 −1.5 −1.7 −1.6  500−1.4 −1.7 −1.7  750 −1.5 −1.7 −1.7 1000 — −1.6 −1.6 1250 — −1.5 −1.51500 — −1.4 −1.3 1750 — −1.5 −1.6 2000 — −1.4 −1.5 2244 — −1.2 −1.2 2478— −1.3 −1.2 2728 — −1.3 −1.2 2978 — −1.1 −1.1 3228 — −1.2 −0.9 3478 —−1.0 −1.0

TABLE 7 Cleveland Humidity Accelerated Weathering 20° Gloss Retention ofComparative and Example Polyurethane Coatings Coating FormulationComparative Example Example Example C1 C2 C3 Polyester Formulation fromExample 1 P1 P3 P4 Mole % TMCD in Polyester 0 100 100 Hours Exposure 20°Gloss 0 65.5 80.3 81.3 24 65.9 80.3 82.1 48 62.9 80 82 148 61.8 79.781.9 288 57.6 80.6 82.2 456 45.4 80.1 81.6 600 46.3 80.4 81.9 768 39.479.5 81.8 936 34.5 76.8 80.3 1104 28.2 77.9 80.6 1272 14.4 77.2 80.21532 13 77.1 79.6 1700 — 76.3 79.7 1868 — 77.2 80.3 2036 — 77.1 80.92252 — 74.9 79.7 2500 — 74.5 79.1 2740 — 75.3 79.1 3004 — 73.7 80.1 3100— 75.4 79.8 3316 — 72.8 79.6 3580 — 71.2 79.8 3820 — 64.7 79.7 4080 —66.9 78.7 4330 — 59.7 78.8 4640 — 54.1 78.4 4928 — 50.1 78.4 5168 — 42.674.8 5418 — 41.4 76.1 5638 — 37 75.6 5854 — 29.2 76.3 6142 — 28.5 73.16430 — 14.1 70.6 6622 — — 71.6 6910 — — 72.7 7390 — — 69.4 7678 — — 69.78086 — — 64.1 9326 — — 60.6 9734 — — 52.4 10046 — — 59.1

TABLE 8 Cleveland Humidity Accelerated Weathering 60° Gloss Retention ofComparative and Example Polyurethane Coatings Coating FormulationCornparative Example Example Example C1 C2 C3 Polyester Formulation fromExample 1 P1 P3 P4 Mole % TMCD in Polyester 0 100 100 Hours Exposure 60°Gloss 0 85.2 87.4 89.8 24 85.3 87.3 89.8 48 84.1 87.4 89.6 148 83.8 87.689.7 288 81.7 87.5 89.7 456 69.3 87.3 89.6 600 68.5 87.3 90.0 768 62.887.5 90.2 936 56.7 85.5 89.0 1104 53.7 85.2 88.0 1272 33.1 85.7 88.51532 28.0 84.9 88.5 1700 — 84.8 87.9 1868 — 85.4 89.5 2036 — 86.2 89.12252 — 84.6 88.3 2500 — 84.9 88.6 2740 — 85.1 88.1 3004 — 85.5 89.0 3100— 85.5 88.6 3316 — 84.6 88.4 3580 — 84.6 90.3 3820 — 81.0 88.9 4080 —82.4 89.0 4330 — 79.3 87.9 4640 — 77.3 88.4 4928 — 74.7 88.0 5168 — 70.387.5 5418 — 70.9 85.9 5638 — 66.4 86.5 5854 — 60.7 86.7 6142 — 61.5 84.66430 — 48.9 84.8 6622 — — 84.9 6910 — — 84.8 7390 — — 82.5 7678 — — 82.98086 — — 80.2 9326 — — 77.8 9734 — — 77.9 10046 — — 78.4

TABLE 9 Cleveland Humidity Accelerated Weathering Blister Rating ofComparative and Example Polyurethane Coatings Coating FormulationComparative Example Example Example C1 C2 C3 Polyester Formulation fromExample 1 P1 P3 P4 Mole % TIVICD in Polyester 0 100 100 Hours ExposureBlister Rating (Size/Density) 0 None/None None/None None/ None 24None/None None/None None/ None 48 None/None None/None None/ None 148None/None None/None None/ None 288 8/Medium None/None None/ None 4566/Medium None/None None/ None 600 4/Medium None/None None/ None 7684/Dense None/None None/ None 936 4/Dense None/None None/ None 11044/Dense None/None None/ None 1272 2/Dense None/None None/ None 15322/Dense None/None None/ None 1700 — None/None None/ None 1868 —None/None None/ None 2036 — None/None None/ None 2252 — None/None None/None 2500 — None/None None/ None 2740 — None/None None/ None 3004 —None/None None/ None 3100 — None/None None/ None 3316 — None/None None/None 3580 — None/None None/ None 3820 — None/None None/ None 4080 —None/None None/ None 4330 — None/None None/ None 4640 — None/None None/None 4928 — None/None None/ None 5168 — 6/Few None/ None 5418 — 6/FewNone/ None 5638 — 6/Few None/ None 5854 — 6/Few None/ None 6142 — 6/FewNone/ None 6430 — 6/Few None/ None 6622 — — None/ None 6910 — — None/None 7390 — — None/ None 7678 — — None/ None 8086 — — None/ None 9326 —— None/ None 9734 — — None/ None 10046 — — None/ None

1. A curable, aliphatic polyester, comprising: i. diacid residues,comprising about 50 to 100 mole percent of a cycloaliphatic dicarboxylicacid; ii. diol residues, comprising about 50 to 100 mole percent, basedon the total moles of diol residues, of the residues of2,2,4,4-tetramethyl-1,3-cyclobutanediol; and iii. about 2 to about 40mole percent of the residues of at least one polyol, based on the totalmoles of diol and polyol residues; wherein said curable, aliphaticpolyester contains 90 or greater mole percent aliphatic diacid residuesbased on the total moles of diacid residues, and wherein said curable,aliphatic polyester has a number average molecular weight of about 300to about 10,000 daltons, a hydroxyl number of about 20 to about 450 mgKOH/g of polyester, and an acid number of 0 to about 80 mg KOH/g ofpolyester.
 2. The curable, aliphatic polyester according to claim 1wherein said diacid residue comprises about 50 to about 100 mole percentof the residues of at least one cycloaliphatic dicarboxylic acid chosenfrom 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid,hexahydrophthalic anhydride, and about 50 to about 0 mole percent of theresidues at least one-acyclic aliphatic dicarboxylic acid chosen fromadipic acid, dodecanedioic acid, sebacic acid, azelaic acid, succinicacid, and glutaric acid; and said diol residues comprise about 50 to 0mole percent of the residues of at least one diol chosen from neopentylglycol, ethylene glycol, propylene glycol, diethylene glycol,triethylene glycol, tetraethylene glycol, pentaethylene glycol,hexaethylene glycol, heptaethylene glycol, octaethylene glycol,nonaethylene glycol, decaethylene glycol, 1,3-propanediol,2,4-dimethyl-2-ethyl-hexane-1,3-diol, 2,2-dimethyl-1,2-propanediol,2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol,1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol,2,2,4-trimethyl-1,6-hexanediol, thiodiethanol,1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol,1,4-cyclohexanedimethanol, 2,2,4-trimethyl 1,3-pentanediol,p-xylenediol, hydroxypivalyl hydroxypivalate, 1,10-decanediol, andhydrogenated bisphenol A.
 3. The curable, aliphatic polyester accordingto claim 2 wherein said diacid residues comprise about 50 to about 100mole percent of the residues of 1,4-cyclohexanedicarboxylic acid,hexahydrophthalic anhydride, or a mixture thereof, and about 0 to about50 mole percent of the residues of adipic acid; and said diol residuescomprise about 50 to 0 mole percent of the residues of neopentyl glycol.4. The curable, aliphatic polyester according to claim 3 wherein saiddiacid residues comprise about 100 mole percent of the residues ofhexahydrophthalic anhydride; and said diol residues comprise, about 50to 100 mole percent of the residues of2,2,4,4-tetramethyl-1,3-cyclobutanediol, and about 50 to 0 mole percentof the residues of neopentyl glycol.
 5. The curable, aliphatic polyesteraccording to claim 1 which comprises about 3 to about 30 mole percent ofthe residues of at least one polyol selected from trimethylolpropane,pentaerythritol, trimethylolethane, erythritol, threitol,dipentaerythritol, sorbitol, and glycerine.
 6. The curable, aliphaticpolyester according to claim 1 which has a Tg of about −35 to about 35°C.
 7. The curable, aliphatic polyester according to claim 1 which has ahydroxyl number of about 30 to about 250 mg KOH/g of polyester, an acidnumber of about 2 to about 15 mg KOH/g of polyester, a number averagemolecular weight of about 700 to about 7000 daltons, and a Tg of about−35 to about 35° C.
 8. A thermosetting coating composition, comprising:(A). about 50 to about 90 weight percent, based on the total weight of(A) and (B) of at least one curable, aliphatic polyester, comprising i.diacid residues, comprising about 50 to 100 mole percent of acycloaliphatic dicarboxylic acid; ii. diol residues, comprising about 50to 100 mole percent, based on the total moles of diol residues, of theresidues of 2,2,4,4-tetramethyl-1,3-cyclobutanediol; and iii. about 2 toabout 40 mole percent of the residues of at least one polyol, based onthe total moles of diol and polyol residues; wherein said curable,aliphatic polyester contains 90 or greater mole percent aliphatic diacidresidues based on the total moles of diacid residues, and wherein saidcurable, aliphatic polyester has a number average molecular weight ofabout 300 to about 10,000 daltons, a hydroxyl number of about 20 toabout 450 mg KOH/g of polyester, and an acid number of 0 to about 80 mgKOH/g of polyester; (B). about 10 to about 50 weight percent, based onthe total weight of (A) and (B) of a crosslinker comprising at least onecompound reactive with a carboxylic acid or a hydroxyl group; (C). about10 to about 60 weight percent, based on the total weight of (A), (B),and (C) of at least one nonaqueous solvent.
 9. The coating compositionaccording to claim 8 wherein said curable, aliphatic polyester comprisesdiacid residues comprising about 50 to about 100 mole percent of theresidues of at least one cycloaliphatic dicarboxylic acid is chosen from1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid andhexahydrophthalic anhydride, and about 50 to about 0 mole percent of theresidues at least one acylic aliphatic dicarboxylic acid chosen fromadipic acid, dodecanedioic acid, sebacic acid, azelaic acid, succinicacid, and glutaric acid; and diol residues comprising about 50 to 0 molepercent of the residues of at least one diol chosen from neopentylglycol, ethylene glycol, propylene glycol, diethylene glycol,triethylene glycol, tetraethylene glycol, pentaethylene glycol,hexaethylene glycol, heptaethylene glycol, octaethylene glycol,nonaethylene glycol, decaethylene glycol, 1,3-propanediol,2,4-dimethyl-2-ethyl-hexane-1,3-diol, 2,2-dimethyl-1,2-propanediol,2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol,1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol,2,2,4-trimethyl-1,6-hexanediol, thiodiethanol,1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol,1,4-cyclohexanedimethanol, 2,2,4-trimethyl 1,3-pentanediol,p-xylenediol, hydroxypivalyl hydroxypivalate, 1,10-decanediol, andhydrogenated bisphenol A.
 10. The coating composition according to claim9 wherein said diacid residues comprise about 50 to about 100 molepercent of the residues of 1,4-cyclohexanedicarboxylic acid,hexahydrophthalic anhydride, or a mixture thereof, and about 50 to about0 mole percent of the residues of adipic acid; and said diol residuescomprise about 50 to 0 mole percent of the residues of neopentyl glycol.11. The coating composition according to claim 8 wherein said curable,aliphatic polyester has a Tg of about −35 to about 35° C.
 12. Thecoating composition according to claim 8 wherein said curable, aliphaticpolyester comprises about 3 to about 30 mole percent of the residues ofat least one polyol selected from trimethylolpropane, pentaerythritol,trimethylolethane, erythritol, threitol, dipentaerythritol, sorbitol,and glycerine.
 13. The coating composition according to claim 8 whereinsaid curable, aliphatic polyester has a hydroxyl number of about 30 toabout 250 mg potassium hydroxide per gram of polyester, an acid numberof about 2 to about 15 mg potassium hydroxide per gram of polyester, anda number average molecular weight of about 700 to about 7000 daltons,and a Tg of about −35 to about 35° C.
 14. The coating compositionaccording to claim 8 wherein said crosslinker comprises at least onecompound chosen from melamines, isocyanates, and isocyanurates.
 15. Thecoating composition according to claim 14 wherein said crosslinkercomprises at least one melamine compound chosen fromhexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine,tetramethoxymethylurea, and mixed butoxy/methoxy substituted melamines.16. The coating composition according to claim 14 wherein saidcrosslinker comprises isocyanurates of 1,6-hexamethylene diisocyanate,the biuret of 1,6-hexamethylene diisocyanate, the trimer of1,6-hexamethylene diisocyanate, or combinations thereof.
 17. The coatingcomposition according to claim 8 wherein said nonaqueous solventcomprises benzene, xylene, mineral spirits, naptha, toluene, acetone,methyl ethyl ketone, methyl n-amyl ketone, methyl isoamyl ketone,n-butyl acetate, isobutyl acetate, t-butyl acetate, n-propyl acetate,isopropyl acetate, ethyl acetate, methyl acetate, ethanol, n-propanol,isopropanol, n-butanol, sec-butanol, isobutanol, ethylene glycolmonobutyl ether, propylene glycol n-butyl ether, propylene glycol methylether, propylene glycol monopropyl ether, dipropylene glycol methylether, diethylene glycol monobutyl ether, trimethylpentanediolmono-isobutyrate, ethylene glycol mono-octyl ether, diacetone alcohol,2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, or combinationsthereof.
 18. A shaped object coated with the coating composition ofclaim 8.